Low foaming detergent



United States Patent 3,215,633 LOW FOAMING DETERGENT Richard Anthony Grifo, Easton, Pa., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware N0 Drawing. Filed Dec. 11, 1953, Ser. No. 397,770 4 Claims. (Cl. 252-152) The present invention relates to a novel detergent composition possessed of unusual foam inhibiting properties as well as excellent surface active properties.

The prevention of foaming in aqueous detergent mediums wherein a surface active agent is employed to effect a cleaning or washing action is highly desirable in many fields of application. Thus, in commercial and industrial processes, such as in metal cleaning operations, in textile processing and finishing, in paper making and the like, and in commercial and industrial establishments, as well as in the home, the suppression or inhibition of foam is not only desirable but absolutely essential to effect a satisfactory cleaning or washing performance. It is well known that in commercial and home type dishwashers the presence of foam materially interferes with the efficiency of the cleansing action of such dishwashers. Further, the presence of foam puts an undesirable and added load on such equipment, rendering the life thereof much shorter than normally contempleted.

It has now been discovered that products having excellent detergent properties without the disability of generating foam can be obtained by the combination of alkylated phenols with surface active agents of the nonionic or cationic type.

An object of the present invention is the provision of new and improved low foaming detergent compositions.

Another object of this invention is the provision of new and improved low foaming detergent compositions which in aqueous mediums are substantially neutral.

A still further object of this invention lies in the use of new and improved low foaming detergent compositions in aqueous mediums to effect a highly eflicient cleansing action.

Still further objects will appear hereinafter.

In accoradnce with the present invention, it has been discovered that alkyl phenols and in particular certain higher alkylated pehnols in combination with non-ionic surface agents, in particular, oxyalkylenated alkyl phenols or that the said alkyl phenols in combination with cationic surface active agents of the quaternary ammonium type result in highly efficient detergent compositions having a low tendency to foam. Such compositions in addition to exhibiting low foaming tendencies and excellent detergency gives substantially a neutral reaction in aqueous mediums. Where corrosion is a serious problem, whether from the basic or acidic substances, the instant compositions may be employed with absolute safety. In addition, the neutrality of the compositions of the present invention renders them particularly safe for handling, especially by the ultimate consumer.

Among the alkalated phenols which have been found particularly effective in the compositions of this invention are:

' Iso-octyl phenol,

Nonylphenol,

Diamylphenol, A C alkylated phenol, and Dinonyl phenol.

p Ce

'Examples of non-ionic surface active agents which are preferred are:

Polyoxyethylenated nonylphenols 0(CH1CH2O)11H W=nony1 radical Polyoxyethylenated lso-octyl phenols O (OHgCHzO)nH X =iso-octyl radical Polyoxyethylenated Cir-alkylated phenols O (OH3CI'I2O)11H Y =alkyl radical Polyoxyethylenated dinonyl phenols O (GHzOHzO) 1113:

W =nonyl radical 7 where rt is a whole number ranging from 7 to 35.

Among the quaternary ammonium compounds found to be particularly effective in the present invention are alkyl dirnethyl benzyl ammonium chlorides 'wherein the alkyl radicals may contain from 8 to I18 carbon atoms.

The relative proportion of surface active agent and alkylated phenol may be varied considerably. While as low as one percent alkylated phenol, based on the weight of the total composition, gives decided foam inhibiting properties to the detergent, the most marked results are obtained in the range of 5 to 20% alkylated phenol. However, continued increasing defoaming action is obtained up to 50% and more alkylated phenol. With respect to the non-ionic surface active agents, it has been found preferable to employ about 7 to 35 moles of alkylene oxide or its equivalent per mole of alkylated phenol in preparing the polyalkoxylated non-ionic surfactant. Of the alkylene oxides or equivalents thereof, ethylene oxide is preferred although other alkylene oxides such as propylene and butylene oxides may be used. Further, it is obvious that in the preparation of the polyoxyalkylenated alkyl phenols, the equivalents of the alkylene oxides which may be employed are, for example, the chlorohydrins and the like.

The following examples will serve to' illustrate the invention, it being understood, however, that the invention is not limited thereto.

EXAMPLE 1 A mixture of 99 parts of a polyoxyethylenated nonyl phenol and 1 part of p-nonyl phenol was prepared.

The polyoxyethylenated nonyl phenol was prepared by the interaction of about 9 moles of ethylene oxide and one mole of commercial nonyl phenol. The latter consists primarily of para-nonyl phenol with minor amounts of ortho-nonyl phenol also being present. The ethylene oxide condensation product may be prepared by any of the methods known in the art, for example, as described in US. Patent 2,213,477 issued to Adolph Steindorff et al., on September 3, 1940.

Two parts of the above described mixture was added to 1000 parts of water. It was observed that the mixture was determined using the Ross-Miles Foam Test (see Oil & Soap, vol. 18, pp. 99-102, 1941), which test is familiar to the detergent field. The results of the test are given in Table 1, item 2. Item 1 in this table shows the results obtained with the surfactant of this example without any added alkylated phenol. The four columns under Height of Foam (cm.), represent the heights at four diiferent times, the height given in the second, third and fourth columns being measured one-half, two minutes and five minutes, respectively, after the original height given in column was measured. It will be observed that the instant mixtures at first produced about two-thirds as much foam as the standard (item 1), but after five minutes only about half as much foam.

EXAMPLES 2-5 Mixtures of the same surfactant and alkylated phenol as described in Example 1 were prepared with the surfactant: alkylated phenol ratio being 95:5, 90:10, 80:20 and 50:50. The results are given in Table I, as items 3-6.

EXAMPLE 6 A 90:10 surfactantzalkylated phenol mixture similar to the one of Example 1 was prepared and tested at a concentration of 0.05% in the Ross-Miles Foam Test. The results are given as item 7 in Table I.

The outstanding anti-foam properties of the instant compositions at such very low concentrations demonstrates clearly that the remarkable improvement herein achieved is directly a function of the combination of surface active agent and defoaming agent.

4 EXAMPLES 7-10 Mixtures were prepared as given in Table I, items 8-11. The results again clearly demonstrate the superior and excellent anti-foaming characteristics of the compositions of the present invention.

EXAMPLES 1 l-13 Mixtures of 10% nonylphenol and surfactant were prepared and tested at a concentration of 0.2%. The surfactants employed were an oxyethylenated C alkyl phenol (prepared from about 15 moles ethylene oxide per mole of C alkyl phenol), an alkyl dimethyl benzyl ammonium chloride and a castor oil-ethylene oxide condensate (prepared from 40 moles ethylene oxide per mole of castor oil) and the results are given as items 12b, 13b and 14b, respectively, in Table I. Items 12a, 13a and 14a represent the control surfactants without any added defoaming agent.

EXAMPLES 14-20 Mixtures of 10% nonyl phenol and 90% surfactant were prepared and tested as above at a concentration of 0.2%. The surfactants employed were:

Example 14.Nonyl phenol condensed with 11 moles of ethylene oxide.

Example 15.Nony1 phenol condensed with 15 moles of ethylene oxide.

Example 16.N0nyl phenol condensed with 30 moles of ethylene oxide.

Example 17.Oleyl alcohol condensed with 20 moles of ethylene oxide.

Example 18.Dinonyl phenol condensed with 17 moles of ethylene oxide.

Example 19.Dinonyl phenol condensed with 35 moles of ethylene oxide.

Example 20.Nonyl phenol condensed with 9 moles of ethylene oxide.

Example 21.p-n-Octylphenol condensed with 7 moles of ethylene oxide.

The results are given in Table I with the corresponding controls containing surfactant alone (i.e., without any added defoaming agent). Items 15a-22a are the controls, and 15b -22b the improved compositions of this invention.

Table l ROSS-MILES FOAM TEST (TAP WATER 25 C.)

Cone Height of Foam (cm.) Ex. Product Item Per- No. No. cent 9N9o7nphe1110i+9 1 0 05 1 0.2 10.0 15.5 14.0 12.5

ony p eno 9 1 3.5 ll x gx l l 12 531;9E O 2 0.2 11.5 11.0 10.0 5.0

yp 2 gg y g g g hgfiz O a 0.2 8.0 7.5 7.0 5.0

ony p eno a "Q85; N g {i9E O 4 0.2 2.5 2.0 1.5 1.5

ny p eno 4 m ilm O 5 0.2 1.0 0.5 0.5 0.5

ony p eno 5 .4385? g f g iigla O 0 0.2 0.5 0.5 0.5 0.5

ony p eno 0 333 N y g ilrgE 0 7 0.05 2.5 2.0 1.5 1.5

ony p eno 7 g y g ilrglm s 0.2 1.5 1.0 1.0 1.0

onyp eno s -.{8g 1 $m O 0 0.2 6.0 4.5 3.0 1.0

ony p eno 9 9,, t g g flrw O 10 0.2 5.0 4.5 4.0 4.0

50-00 y p eno 10 11 0.2 2.5 2.0 2.0 1.5 glgAl yllx igerlioll+ltlfiitli 0 12a 0.2 10.0 15.0 14.0 13.0

y p eno 11 12b 0.2 1.0 1.0 1.0 1.0 Alkyl Dlmethyl Benzyl Ammomum Chloride 1 13a 0. 2 14. 0 13.0 11.0 10.0

See footnotes at end of table.

- Table IContinued Conc Height of Foam (cm.) Ex. Product Item Per- I No. l No cent 3 %I 2! 5! 00 7 .Alk lDimeth lBenz lAmmonium 011101155 12 Y Y }135 0.2 3.5 2.0 1.0 0.5 50 1 11+ 40 1t. 14a 0. 2 7. 0 6. 5 5. 5 4. 5

as or i 0 r 13 3 jg. 145 0.2 2.0 1.0 0.5 0.5 go7n3lGphe111o+111i(1) E 6 155 0. 2 15. 1 14. 9 14. 5 14. 5

0 ony p eno 14 Nonylphenol }150 0.2 2.7 2.7 2.7 2.0 7nlphe111ol1+151 .1O.E b 16a 0. 2 15. 0 14. 5 14. 4 7. 3

onyp eno 6 Z }105 0.2 0.7 0.3 0.3 5.9 Nonylphenol+ E.O 17a 0. 2 14. 3 14. 0 13. 7 12. 9 10 :}170 0.2 10.2 10.0 10.0 10.0 g)lyi)ii.lctihtil+gOlE.2(g fi b 1811 0.2 10.2 10.0 9.8 9.5

e 800 0 17 g }1s5 0.2 4.9 4.8 4.7 4.7 ggaogylphenoll-kfllfi .1756 19a 0. 2 s. 5 8.2 8. 1 7. 0

0 inony p eno 1s {10.ZNony1pheno1 190 0.2 1.5 1.5 1.4 1.4 i7r 1o1r)1y1pher11o%]+351E.3Ofi O 20a 0. 2 10. 4 10. 0 9. 6 9. 6

inon eno 5 19 g }200 0.2 4.8 4.5 4.5 4.3 gggn hez wfie 3. 21a 0. 2 12. 5 12. 3 11. 0 11. 9

ony eno 20 s; i }210 0.2 4.4 4.3 4.1 3.0 SEgg/1:0cty(l)pl%e111o%1|7 113.9356. 22a 0. 2 10. 0 10. 0 9. 5 9.0

-11- 0 y eno 21 3 gonylnhegm }220 0.2 4.0 3.7 3.5 3.2

1 E.O.=Moles of ethylene oxide. 1 0 to 0 a 2.0 grams/liter.

As a further demonstration of the value of the comhalide surface active agent, and from about 1% to positions of the present invention, a comparison of surface active properties is set forth between an unmodified surfactant and the same substance to which 10% defoamer has been added. This composition is similar to the one above described in Example 3. The results shown in Table II demonstrate that the surfactantdefoamer mixture is substantially as good for its surface active properties as the surfactant when used alone.

Table II Draves Surface Tension Interracial Tension Wetting (dynes/cm.) gm./l. (dynes/cm.) gm./l. Product Test 1 25 Sec Wetting, 10. 0 l. 0 1 01 10. 0 1. 0 1 01 gm./l.

Nony1phenol+E.O 0.35 31.0 31.0 31.0 42.0 2. 7 2. 7 5.3 17.0 10% Nonylphenol, 90% Nonylphenol-i-E. 0.40 29.0 28. 0 28.0 36.0 1. 0 2. 0 6.0 16.0

1 Technical Manual and Yearbook, American Association of Textile Chemists and Colorists, vol. XXV (1949),

pages 1435; also vol. XXVI (1960), pages 139-42.

4. The composition of claim 3 wherein there is present 10% nonyl phenol as the alkylated monohydric phenol.

References Cited by the Examiner UNITED STATES PATENTS 2,213,477 9/40 Steindorf et al 252--89 XR 2,258,556 10/41 Schirm 1673l 2,264,150 11/41 Hueter et al. 16731 (Other references on following page) 7 UNITED STATES PATENTS Read 167-31 Tremain et a1. 252-156 Soule et a1. 252-106 Kinney 252-106 XR 5 Sarchet 252-89 Fineman 252-89 '8 FOREIGN PATENTS 663,565 12/51 Great Britain.

JULIUS GREENWALD, Primary Examiner.

GEORGE A. GOREOKI, JOSEPH R. LIEBERMAN,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,215,633 November 2, 1965 Richard Anthony Grifo It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 22, for "Y=alkyl radical" read Y=C alkyl radical columns 5 and 6, Table II first column, line 1 thereof, for "Nonylphenol+E.O" read Nonylphenol+9 E same table, same column, line 2 thereof, for "10% Nonylphenol, 90% N0nylphen01+E.O" read 10% Nonylphenol, 90 Nonylphenol+9 E.O

Signed and sealed this 18th day of October 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENF Attesting Officerl I Commissioner of Pate: 

1. A COMPOSITION HAVING REDUCED FOAMING CHARACTERISTICS AND BEING SUBSTANTIALLY NEUTRAL IN AQUEOUS SYSTEMS CONSISTING ESSENTIALLY OF A CATIONIC QUATERNARY AMMONIUM HALIDE SURFACE ACTIVE AGENT, AND FROM ABOUT 1% TO 50% OF AN ALKYLATED MONOHYDRIC PHENOL HAVING FROM 8-18 CARBON ATOMS IN THE ALKYL RADICAL. 